In 1996 Zubkov F.I. graduated from the Peoples' Friendship University of Russia named after Patrice Lumumba, Chemistry department.
In 2000 he defended his thesis for Ph.D. degree on "Synthesis of substituted and spiroannelated benz-2-azepines, 1,2,3-oxathiazine-2,2-dioxides, azetidines, 7-oxa-1-azabicyclo [2.2.1] heptanes and 6-phenylpiperidin-4-ol based on homoallylamines and their nitrones. Study of the [3 + 2] cycloaddition of alkenes to the N-oxide" and was awarded the Ph.D. degree in Chemistry.
In 2007 he was awarded the academic title of Associate Professor in the Department of Organic Chemistry, the Faculty of Science, Peoples' Friendship University of Russia (RUDN University).
Lecturing experience
15-years of lecturing at the RUDN University.
Lecture courses in chemistry for 2-6th year students:
- organic chemistry;
- stereochemistry;
- the strategy of organic synthesis;
- the basis of nuclear magnetic resonance;
- supervision of conducting scientific research practice with candidates for a master's degree.
Research
New approaches to the construction of heterocyclic systems with an isoindole fragment based on IMDAF and IMDAV reactions were discovered. Original methods for the synthesis of partially hydrogenated quinolines, isoquinolines and benzazepines have been developed. Scientific works contributed to the understanding of the intramolecular [4 + 2] cycloaddition reaction mechanism and stereochemistry in the furan series.
Grant support of scientific research:
- project manager of the Russian Foundation for Basic Research;
- two-time holder of Potanin’s grants and the Moscow government's "Best Teacher" (2004, 2006);
- author of more than 100 publications in international scientific journals;
- Hirsch index 15 (Scopus).
Research interests
Various aspects of the chemistry of heterocyclic compounds: synthesis, stereochemistry, dynamics, reaction mechanisms. The greatest number of publications is devoted to the transformation of furan, isoindole and intramolecular Diels-Alder reaction.
NOVEL APPROACH TO ISOINDOLO[2,1-a]QUINOLINES: SYNTHESIS OF 1- AND 3-HALO-SUBSTITUTED 11-OXO-5,6,6A,11-TETRAHYDROISOINDOLO[2,1-a]QUINOLINE-10-CARBOXYLIC ACIDS
Boltukhina E.V., Zubkov F.I., Nikitina E.V., Varlamov A.V.
Synthesis. 2005. № 11. С. 1859-1875.
DOI: 10.1055/s-2005-869948
Abstract:
A series of 1- and 3-halo-substituted isoindolo[2,1-a]quinolines were obtained by means of electrophilic cyclization of methallyl- and allyl-substituted isoindolo-7-carboxylic acids. The influence of halogen atoms on the stereochemistry of the formation of key intermediates, 3a,6-epoxyisoindoles, was studied.
AN EFFICIENT SYNTHESIS OF ISOINDOLO[2,1-a]QUINOLINE DERIVATIVES VIA IMINO DIELS-ALDER AND INTRAMOLECULAR DIELS-ALDER REACTIONS WITH FURAN
Kouznetsov V.V., Cruz U.M., Zubkov F.I., Nikitina E.V.
Synthesis. 2007. № 3. С. 0375-0384.
DOI: 10.1055/s-2007-965875
Abstract:
The straightforward synthesis of new isoindolo[2,1-a]quinoline derivatives from 2,4-disubstituted 1,2,3,4-tetrahydroquinolines bearing a furan fragment via the intramolecular Diels-Alder reaction is reported. The synthesis of key precursors was realized with excellent levels of diastereoselectivity either by Povarov reaction or by a multicomponent condensation approach.
THERMAL AND CATALYTIC INTRAMOLECULAR [4 + 2]-CYCLOADDITION IN 2-ALKENYLFURANS
Zubkov F.I., Nikitina E.V., Varlamov A.V.
Russian Chemical Reviews. 2005. Т. 74. № 7. С. 639-669.
DOI: https://doi.org/10.1070/RC2005v074n07ABEH001180
Abstract:
The published data on the intramolecular Diels–Alder reaction in compounds of the 2-alkenylfuran series are generalised. The methods and conditions for the preparation of tricyclic systems are considered. The effects of the substituents in the furan and the unsaturated fragments on the cycloaddition are discussed. The application of this reaction to the synthesis of alkaloids and terpenoids is exemplified.
EXPERIMENTAL EVIDENCE FOR INTRAMOLECULAR IPSO SUBSTITUTION OF ALKYL GROUPS
Zubkov F.I., Nikitina E.V., Kouznetsov V.V., Duarte L.D.A.
European Journal of Organic Chemistry. 2004. № 24. С. 5064-5074.
DOI: 10.1002/ejoc.200400356
Abstract:
An acid-mediated intramolecular Friedel−Crafts intramolecular alkene alkylation of the ortho-alkyl group in the N-arylamino moiety of various N-(1-allylcycloalkyl)-N-arylamines resulting in alkyl-substituted 3′,4′-dihydro-1′H-spiro[cycloalkane-1,2′-quinolines] is described. The mechanistic details of this intramolecular Friedel−Crafts alkylation by an alkene moiety can be explained by an intramolecular alkylation with ipso substitution of alkyl groups and their 1,2-rearrangement. The scope and limitations of this reaction were determined. As a conclusive proof of the proposed mechanism, previously unknown interesting by-products, dispiro[quino[6,7-f]quinoline-3,1′:9,1′′-bis(cycloalkanes), were isolated and characterized.
WAGNER-MEERWEIN SKELETAL REARRANGEMENT OF 3-SPIROANNULATED 6,8A-EPOXY- AND 6,8a;7,8-DIEPOXYISOQUINOLINES (3-AZA-11-OXATRICYCLO[6.2.1.01,6]UNDEC-9-ENES). ISOLATION AND IDENTIFICATION OF 5-AZA-2-OXATRICYCLO[6.2.1.03,9]UNDEC-3-ENES
Zubkov F.I., Nikitina E.V., Safronova A.A., Borisov R.S., Varlamov A.V., Turchin K.F., Aleksandrov G.G.
Journal of Organic Chemistry. 2004. Т. 69. № 2. С. 432-438.
DOI: 10.1021/jo0353684
Abstract:
The reactions of 3-acetyl-3-aza-11-oxatricyclo[6.2.1.01,6]undec-9-ene and its 9,10-epoxy derivative with bromine and Ac2O/BF3·OEt2 under different conditions were studied. Unusual products of Wagner−Meerwein rearrangement bearing the olefin fragment (5-aza-2-oxatricyclo[6.2.1.03,9]undecen-3-enes) were isolated and characterized by X-ray analysis.
AN IMPROVED AND STEREOSELECTIVE ROUTE TO ALL-CIS-2,6-DISUBSTITUTED 4-HYDROXYPIPERIDINES FROM ACCESSIBLE 4-SUBSTITUTED 4-N-BENZYLAMINOBUT-1-ENES
Varlamov A., Kouznetsov V., Zubkov F., Chernyshev A., Shurupova O., Vargas Méndez L.Y., Palma Rodríguez A., Rivero Castro J., Rosas-Romero A.J.
Synthesis. 2002. № 6. С. 771-783.
DOI: 10.1055/s-2002-25770
Abstract:
The reaction between allylmagnesium bromide and imines 5a-l leads to the corresponding 4-substituted 4-N-benzylaminobut-1-enes 6a-l, which were oxidized in a regioselective manner to the alkenylnitrones 7a-l. The intramolecular 1,3-dipolar cycloaddition of these nitrones gave 2-spiroannulated or 2-substituted 6-exo-phenyl-1-aza-7-oxabicyclo[2.2.1]heptanes 8a-j. Reductive cleavage of the N-O bond of the obtained bicycles afforded the diverse substituted 4-hydroxypiperidines 9a-h in good yields. This stereoselective approach allowed the preparation of all-cis-4-hydroxy-6-phenyl-2-nonylpiperidine (9i), a close analogue of dendrobatid frog alkaloid 241D.
EFFICIENT SYNTHESIS AND SPECTROSCOPIC ANALYSIS OF 8-NITRO SPIRO C-3-ANNULATED 2-BENZAZEPINES AND THEIR N-OXIDES
Varlamov A., Zubkov F., Chernyshev A., Alexandrov G., Kouznetsov V., Palma A., Vargas L., Salas S.
Synthesis. 2001. № 6. С. 849-854.
DOI: 10.1055/s-2002-25770
Abstract:
The reaction between allylmagnesium bromide and imines 5a-l leads to the corresponding 4-substituted 4-N-benzylaminobut-1-enes 6a-l, which were oxidized in a regioselective manner to the alkenylnitrones 7a-l. The intramolecular 1,3-dipolar cycloaddition of these nitrones gave 2-spiroannulated or 2-substituted 6-exo-phenyl-1-aza-7-oxabicyclo[2.2.1]heptanes 8a-j. Reductive cleavage of the N-O bond of the obtained bicycles afforded the diverse substituted 4-hydroxypiperidines 9a-h in good yields. This stereoselective approach allowed the preparation of all-cis-4-hydroxy-6-phenyl-2-nonylpiperidine (9i), a close analogue of dendrobatid frog alkaloid 241D.
COPPER(II) ARYLHYDRAZONE COMPLEXES AS CATALYSTS FOR C[SBND]H ACTIVATION IN THE HENRY REACTION IN WATER
Ma Z., Gurbanov A.V., Kopylovich M.N., Mahmudov K.T., Pombeiro A.J.L., Maharramov A.M., Guseinov F.I., Zubkov F.I.
Journal of Molecular Catalysis A: Chemical. 2017. Т. 426. С. 526-533.
DOI: 10.1016/j.molcata.2016.05.030
Abstract:
Three new water-soluble copper(II) complexes [Cu(HL)(H2O){(CH3)2NCHO}] (1), [Cu(H2L)2(im)4]·CH3OH (2) and [Cu(HL)(CH3OH)]2(μ2-py) (3) were synthesized from copper(II) nitrate and sodium (Z)-2-(2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)hydrazinyl)benzene-sulfonate (NaH2L), in the absence (for 1) and presence of imidazole (im) (for 2) or pyrazine (py) (for 3), and fully characterized. The complexes 1–3 have been tested as stereoselective CH activating catalysts for the model nitroaldol (Henry) condensation of nitroethane with various aldehydes in water. 1 was the most active catalyst affording 64−87% yields with syn/anti diasteroselectivities up to 77:23.
A TWO-STAGE SYNTHESIS OF 8,10a-EPOXYPYRIDO[2,1-a]ISOINDOLES: STEREOCHEMISTRY OF THE [4+2] CYCLOADDITION OF MALEIC ANHYDRIDE WITH 2,6-DIFURYLPIPERIDIN-4-ONES
Zubkov F.I., Airiyan I.K., Zaytsev V.P., Nikitina E.V., Varlamova A.V., Turchin K.F., Gurbanov A.V., Maharramov A.M., Khrustalev V.N., Peregudov A.S.
Synthesis. 2009. № 24. С. 4235-4255.
DOI: 10.1055/s-0029-1217033
Abstract:
A new straightforward synthesis of 8,10a-epoxypyrido[2,1-a]isoindoles and their 7-carboxylic acids from 2,6-difuryl-substituted piperidin-4-ones and maleic anhydride or acryloyl chloride via the intramolecular Diels-Alder reaction has been demonstrated. It has been shown that a one-stage synthesis of the title compounds can be performed under mild conditions and with high levels of regio- and stereoselectivity from easily accessible 2-furylpiperidines.
AROMATIZATION OF IMDAF ADDUCTS IN AQUEOUS ALKALINE MEDIA
Zubkov F.I., Airiyan I.K., Ershova J.D., Galeev T.R., Zaytsev V.P., Nikitina E.V., Varlamov A.V.
RSC Advances. 2012. Т. 2. № 10. С. 4103-4109.
DOI: 10.1039/C2RA20295F
Abstract:
In this paper, we propose a simple synthesis of isoindoline-4-carboxylic acids by means of the aromatization of 3a,6-epoxyisoindoles in alkaline media. The method is facile from an experimental point of view: a short-term (0.5–2h) reflux of epoxyisoindoles in 5% aqueous solutions of alkali leads to the target products in 40–90% yields. The absence of by-products, ease of isolation of the target products and applicability to acidophobic group bearing substrates favorably distinguishes the proposed procedure from previously utilized acid-catalyzed methods. The proposed strategy has been successfully utilized for isoindole containing compounds and nuevamine-type alkaloids.
EASY CONSTRUCTION OF FURO[2,3-F]ISOINDOLE CORE BY THE IMDAV REACTION BETWEEN 3-(FURYL)ALLYLAMINES AND α,β-UNSATURATED ACID ANHYDRIDES
Zubkov F.I., Zaytsev V.P., Mertsalov D.F., Nikitina E.V., Varlamov A.V., Horak Y.I., Lytvyn R.Z., Homza Y.V., Obushak M.D., Dorovatovskii P.V., Khrustalev V.N.
Tetrahedron. 2016. Т. 72. № 18. С. 2239-2253.
https://doi.org/10.1016/j.tet.2016.03.023
Abstract:
The vinylogues of furfurylamines, easily available in two steps from furylacroleins (3-(furyl)allylamines), were studied in a tandem N-acylation/intramolecular [4+2] cycloaddition with maleic, pyrocinchonic, and citraconic anhydrides, as well as furylacryloyl and cinnamoyl chlorides. By using a domino reaction of 3-(furyl)allylamines and α,β-unsaturated acid anhydrides under mild conditions, various hexahydro-4H-furo[2,3-f]isoindoles and their carboxyl derivatives were synthesized efficiently. The domino sequence includes three steps: acylation of the nitrogen atom in 3-(furyl)allylamines, intramolecular Diels–Alder cycloaddition in the resulting N-acyl vinylfurans (IMDAV reaction), and prototropic shift of the adducts followed by recovery of aromaticity of the furan nucleus. The key step, IMDAV reaction, leads to the target products, furo[2,3-f]isoindoles, diastereoselectively and with relatively high yields.